Physical Sciences and Mathematics Commons^™

Reconstructing Surface Water Carbonate Ion Concentration Changes In The Eastern Equatorial Pacific Across Glacial Transitions, Lenzie Gail Ward

OES Theses and Dissertations

Today, the eastern equatorial Pacific (EEP) plays a critical role in the global CO₂ budget as a major source of CO₂ to the atmosphere, but recent studies suggest the region may shift to a sink for atmospheric CO₂ under different climate states. Here, I focus on two transitional periods, the last deglaciation (25 kyr to present) and last glaciation (the Marine Isotope Stage (MIS) 5a-4 transition, 96 to 60 kyr), to investigate how the carbon system in the EEP responds to major climate changes. I measured B/Ca ratios in the planktic foraminifera Globigerina bulloides from core MV1014-17JC …

Sodium-Calcium Ratios In The Planktic Foraminifera Trilobatus Sacculifer As A Proxy For Sea Surface Salinity, Colton Steele Watkins

OES Theses and Dissertations

Recent culture and field studies have found a significant positive correlation between seawater salinity and the incorporation of sodium into foraminiferal calcite, suggesting a potential new proxy for reconstructing past changes in sea surface salinity (SSS) (Mezger et al., 2016 and Bertlich et al., 2018). In order to test the applicability of this new proxy in an open-ocean setting, Na/Ca ratios in the planktic foraminifera Trilobatus sacculifer (T. sacculifer Na/Ca) were measured from a suite of sediment core tops spanning a natural salinity gradient from the North Atlantic subtropical gyre to the South Atlantic subtropical gyre. Initial results from …

Structural Characterization Of Organic Matter In Oil Shales Using Multiple Nuclear Magnetic Resonance Spectroscopic Techniques, Wenying Chu

Chemistry & Biochemistry Theses & Dissertations

Oil shale is a promising source of hydrocarbon fuel that is distributed throughout the world. The petroleum generating potential of oil shale is related to the molecular structure of the organic matter in source rock. The major fraction of organic matter of oil shale is termed kerogen, and due to its insolubility in organic solvents, ¹³C solid-state nuclear magnetic resonance (NMR) spectroscopy is one of the best ways to directly measure the insoluble organic matter without changing its chemical structures. This dissertation investigated oil shale samples using advanced solid-state ¹³C NMR spectroscopy techniques and high resolution magic angle …

The Evolution Of The El Niño-Southern Oscillation And Tropical Pacific Climate Across The Last Deglaciation, Ryan Hunter Glaubke

OES Theses and Dissertations

The El Niño – Southern Oscillation (ENSO) is the largest interannual component of Earth’s climate system, capable of exerting significant influence over global climate patterns that affect communities around the globe. Nevertheless, a comprehensive understanding of the ENSO system and its relationship to tropical Pacific climate dynamics remains unclear. Although new paleoceanographic proxies have shown promise in in their ability to constrain past ENSO change, little is known about how ENSO varied in response to millennial-scale climate events over the last 25,000 years. Here, I present new records of tropical Pacific mean state and ENSO variability over the last 25,000 …

Advances In Amino Acid Analysis For Marine Related Matrices And Its Application To Coastal Shelf Settings In The Canadian Arctic, Rachel M. Mcmahon

OES Theses and Dissertations

Amino acids comprise up to 50% of organic matter in cellular material and are a major fraction of oceanic organic carbon. Amino acids are also considered highly labile during organic matter recycling, making them useful proxies for organic carbon cycling. Nevertheless, analysis of individual amino acids has been burdened by lengthy derivatization and complex analysis since the 1950s. In this thesis, I describe the modification of advanced analytical techniques, developed in the biomedical field, for analysis of marine matrices which allow the determination of at least 40 amino acids without the need for lengthy sample preparation and derivatization, twice the …

Selenium Distribution And Cycling In The Eastern Equatorial Pacific Ocean, Zoe Wambaugh

OES Theses and Dissertations

Oxygen minimum zones in oceanic waters have become increasingly important to the marine environment and society. Low oxygen waters affect not only the distribution and abundance of marine organisms, but also impact the solubility and transport of trace elements that are of biological importance, with the chemical speciation and solubility depending on the actual redox poise of the waters. One redox sensitive trace element of interest is selenium, which can be both toxic and essential for organisms, depending on its chemical speciation. In 2013, the US GEOTRACES program completed the GP16 transect from Peru to Tahiti, going through the oxygen …

Alicyclic And Aromatic Carboxylic Acids In Soil Organic Matter: An Investigation Of Potential Origin And Association With Plutonium Using Advanced Analytical Techniques, Nicole Didonato

Chemistry & Biochemistry Theses & Dissertations

Carboxylic acids are a defining component of soil organic matter, responsible for many of the physical and chemical properties, including metal-organic matter interactions, which govern its role as an important constituent of soils. However, there is a shortage of detailed molecular level information regarding orientation and structural arrangement of carboxylic acids within soil organic matter. This dissertation utilizes electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICRMS) as well as solid-state and multi-dimensional nuclear magnetic resonance (NMR) to investigate the molecular formula composition within several organic matter sources and the primary structures that feature carboxylic acids. Soil organic matter …

Low-Temperature Artificial Maturation Studies Of Type Ii And Type Iii Kerogens: Implications For Biogenic Gas Production, Albert Willy Nguena Kamga

Chemistry & Biochemistry Theses & Dissertations

Ancient organic matter (OM) in shales and coals, known mainly as Type II and Type III OM are known to produce both biogenic, thermogenic gas and oil. In this dissertation, mild artificial maturation, via closed system pyrolysis, is employed to determine the thermal reactivity of Type II and Type III OM beyond diagenesis. We select three Type II kerogens: i) Type II kerogen isolated from recent cores (3.3 Ma, Ro = 0.28) recovered from an upwelling basin in Namibia, Africa referred to as ODP Sediment, ii) Type II-S isolated from sediments (150 Ma, Ro = 0.38) recovered from an outcrop …

Investigation Of The Potential For Algaenan To Produce Hydrocarbon Based Fuels From Algae By Hydrous Pyrolysis, Wassim Adel Obeid

Chemistry & Biochemistry Theses & Dissertations

The use of algae as a feedstock for hydrous pyrolysis has a high potential for producing biofuels. The non-food nature of algae in addition to the various advantages associated with the hydrous pyrolysis process makes this combination for the production of biofuels of high interest. However, current results from algae processing have alluded to some challenges: byproducts arising from the thermal transformation of carbohydrates and proteins, which become incorporated in the oil fraction, result in high oxygen and nitrogen contents of the oil. Accordingly, this produces an oil of low quality for refineries. This dissertation investigates use of a pretreatment …

Molecular Characterization And Photochemical Transformation Of Dissolved Organic Matter From Land To Ocean, Hongmei Chen

Chemistry & Biochemistry Theses & Dissertations

Molecular characterization and photochemical transformation of dissolved organic matter (DOM) in both rivers and the ocean is the main research focus of this dissertation. Chemical characterization of DOM is hampered by the limited application of advanced techniques to desalt, concentrate, isolate and then molecularly characterize DOM. An affordable, commercially available mini-electrodialysis (mini-ED) system has been evaluated and recommended for the efficient desalting of small volume samples of seawater prior to analysis by electrospray Fourier transform ion cyclotron resonance mass spectrometry (ESI FTICR-MS).

A high-recovery technique of DOM isolation – reverse osmosis coupled with electrodialysis (RO/ED) – was used to isolate …

Spectroscopic Characterization Of Dissolved Organic Matter: Insights Into The Linkage Between Sources And Chemical Composition, Xiaoyan Cao

Chemistry & Biochemistry Theses & Dissertations

This dissertation investigated the chemical structure of DOM by advanced solid-state nuclear magnetic resonance (NMR) spectroscopy and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) techniques, as well as isotopic measurements and UV-visible spectroscopy, to shed light on the linkages between DOM sources and DOM composition. Unique and extensive sets of DOM samples studied here were isolated from various aquatic systems, covering end-member environments in which DOM is considered either microbially derived or terrestrially derived, and areas in which DOM has characteristics intermediate between the two end members. Important insights into specific site-related questions were also gained such as …

Molecular Characteristics Of The Water Soluable Organic Matter In Size Resolved Aerosols Collected Over The North Atlantic Ocean, Sarah Catherine Gurganus

Chemistry & Biochemistry Theses & Dissertations

Aerosol particulate matter is acknowledged to have effects on health and the environment and further investigation into the molecular characteristics of aerosols is necessary in order to fully understand the potential links between the molecular characteristics and the impacts that these particles have on health and the environment. Aerosols are often discussed with reference to their size because particles of different sizes can often be associated with different primary sources. This study presents a molecular-level chemical characterization of the water soluble organic matter fraction of 17 aerosol impactor samples representing 3 air mass influences (North American, North African, and marine) …

A New Phase Speciation Leaching Procedure For The Determination Of Metals In Oxic And Anoxic Sediments, Brandon R. Gipson

OES Theses and Dissertations

Toxic trace elements such as cadmium, lead, chromium, and arsenic released by human activities can accumulate in marine and estuarine sediments, where these metals are often sequestered until local environmental changes (e.g., redox, salinity, and/or pH) allow these elements to be reintroduced into the food web. In order to assess the extent of toxic trace element contamination in sediment, numerous leaching schemes have been developed that separate sediment-bound trace metals into operationally defined geochemical phases. These "phase speciation" leaching schemes are typically designed with the purpose of being used on either oxic or anoxic sediments. However, natural sediments often contain …

The Nature, Origin And Preservation Of Amide Organic Nitrogen In Organic Matter, Georgina Anne Mckee

Chemistry & Biochemistry Theses & Dissertations

Past studies have found much of nonliving sedimentary/aqueous nitrogen-containing organic matter (NCOM) is composed of amides, assumed to be peptides/proteins. Their lability calls into question their survival, and several hypotheses have been suggested to explain this. Using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) and nuclear magnetic resonance (NMR) spectroscopy I investigated the molecular amide composition in sedimentary/aqueous systems while reassessing their preservation and formation routes.

Development of a suitable methodology is essential for successful NCOM study due to electrospray ionisation source requirements: sediment samples need to be rendered into solution. Based on NMR and FT-ICR-MS analysis, I determined …

Insights Into Chemical Structure Changes Of Kerogen From Bituminous Coal In Response To Dike Intrusions Investigated By Advanced Solid-State 13C Nmr, Yuan Li

Chemistry & Biochemistry Theses & Dissertations

Variations in the chemical structures of kerogens From highly volatile bituminous coal located near two igneous dike intrusions in the Illinois Basin were examined in detail by advanced solid-state ¹³C nuclear magnetic resonance (NMR) spectroscopy. Spectral-editing techniques were used to identify specific functional groups. Direct polarization was used to quantify different functional groups. ¹H-¹³C two- dimensional heteronuclear NMR was used to examine connectivities and proximities, and ¹H-¹³C long-range recoupled dipolar dephasing was used to estimate aromatic cluster sizes. With decreasing distance to dike contacts and increasing thermal maturity (vitrinite reflectance R₀ from …

Comparison Of Ice Core Dissolved Organic Matter From A Greenland Ice Core By Nanospray Fourier Transform Ion Cyclotron Resonance Mass Spectrometry, Joshua Jeremiah Shiloh Marsh

Chemistry & Biochemistry Theses & Dissertations

Recent studies of ice cores have embarked on the task of determining the classes of dissolved organic matter (DOM) present in melt-water from the cores collected in numerous locations in the northern and southern hemispheres. This DOM originally derives from wet precipitation and is thought to reflect atmospheric organic matter derived from anthropogenic and non-anthropogenic sources. Because the amount of DOM is so low, previous studies have necessarily used large sample volumes (greater than 500 mL) to concentrate sufficient ice core DOM necessary for mass spectral analysis. Solid phase extraction (SPE) with C₁₈ resins was followed by evaporative concentration …

Trace Metal Biogeochemistry In The Western North Pacific, Peter Lynn Morton

OES Theses and Dissertations

Dissolved and suspended particulate samples collected during the Intergovernmental Oceanographic Commission 2002 Contaminant Baseline Survey were analyzed to determine the surface and vertical distributions of Cd, Co, Cu, Mn, Ni Zn and Pb across the western and central North Pacific.

Dissolved trace metal concentrations were measured using a novel isotope dilution-ICP-MS method after extraction over an 8-hydroxyquinoline resin column and validated through the use of the SAFe consensus reference materials. Filtered suspended particulate matter was digested using an HCl/HNO3/HF mixture and analyzed by HR-ICP-MS to obtain total particulate concentrations for the trace metals and other tracer elements such as Al, …

Biogenic Tracers Through The Holocene On The Alaskan Shelf, Carie A. Curry

OES Theses and Dissertations

Dramatic environmental changes in the Arctic Ocean have been observed for the last two decades including changing the amount of sea ice thickness and extent, and increased river discharge. In order to put these and other current day observations into historical context and perhaps reveal mechanisms controlling them, a suite of paleo-proxies were used to analyze two high resolution cores collected on the 2005 HOTRAX expedition. The goals of this research were: (1) develop an analytical method for determining biogenic calcite, (2) identify the major sources of biogenic matter into the system over the Holocene, and (3) assemble the history …

Export Of Terrestrial Dissolved Organic Matter Along A River To Ocean Transect Of The Lower Chesapeake Bay Investigated By Advanced Analytical Techniques, Rachel Leigh Sleighter

Chemistry & Biochemistry Theses & Dissertations

Ultrahigh resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS) has proved essential for the complete separation of the thousands of peaks present in natural organic matter (NOM), a complex assemblage of organic molecules present in water, soils, and sediments. An improved understanding of its composition is crucial to understand how pollutants interact with NOM and how NOM cycles through global carbon cycles.

Optimizing the acquisition and handling of the FTICR mass spectra is the first step to obtaining high quality data. A simple method to internally calibrate the peaks in the complex spectra, using naturally present fatty …

Seagrass-Mediated Carbonate Dissolution And Early Diagenesis In Bahamas Bank Sediments, Xinping Hu

OES Theses and Dissertations

This dissertation presents the results of studies examining the role that seagrasses play in carbonate dissolution and early diagenesis of Bahamas Bank sediments. Three aspects of this problem are addressed: (1) stable carbon isotopes as an indicator of early diagenesis of carbonates, using results of a field study; (2) carbonate dissolution stoichiometry and carbonate reprecipitation, using the results from closed-system sediment incubation studies; (3) carbonate dissolution and reprecipitation across the broader Bahamas Bank. In Chapter II, I examined δ¹³C in the dissolved inorganic carbon (DIC) of sediments with various degrees of seagrass densities. In low seagrass density and …

Anthropogenic Lead Deposition And Four National Parks In Poland As Determined By Lead Isotope Ratios, Shannon Simcoe

OES Theses and Dissertations

Polluted soils are recognized by having high concentrations of heavy metals, including Pb. Partitioning of metals in geochemical fractions, by sequential chemical extractions, may indicate whether a metal has been recently deposited in the soil. While concentration levels alone cannot distinguish between natural and anthropogenic Pb, studies have demonstrated that anthropogenic pollution is accurately recorded by specific Pb isotope signatures, which differ from natural Pb isotopes. The objective of this project was to use ²⁰⁶Pb/²⁰⁷Pb and ²⁰⁶Pb/²⁰⁴Pb isotope ratios to differentiate between the anthropogenic Pb input and the naturally occurring Pb in four national …

Relating Water And Otolith Chemistry In Chesapeake Bay, And Their Potential To Identify Essential Seagrass Habitats For Juveniles Of An Estuarine-Dependent Fish, Spotted Seatrout (Cynoscion Nebulosus), Emmanis Dorval

Biological Sciences Theses & Dissertations

A quantitative understanding of habitat use of estuarine-dependent fishes is critical to the conservation of their most essential habitats. Because recruitment and fitness may be influenced by the quality of juvenile habitats, developing methods to quantify habitat-specific survivorship is pivotal to such understanding. An initial step to quantify survivorship is to validate the habitat-specific natural tags contained in otoliths. To this aim I investigated the variability in the chemistry of surface waters and otoliths of juvenile spotted seatrout, Cynoscion nebulosus, in five seagrass habitats of Chesapeake Bay, namely: Potomac, Rappahannock, York, Island, and Eastern Shore. I measured Mg, Ca, …

Dissolved Humic Substances: Characterization Of Their Sorption Onto Iron Hydroxide Aluminum Hydroxide Kaolinite And Smectite, Sarah E. Diebel

OES Theses and Dissertations

Humic (HA) and fulvic (FA) acids participate in many geochemical processes and the mechanisms of their sorption to colloidal surfaces are numerous, indicating these substances are complex and heterogeneous. The current study focuses on the interactions of the Fe hydroxide (FE), Al hydroxide, Kaolinite (KA) and Smectite (SM) and these naturally occurring organic acids using Fourier Transform Infrared Spectroscopy (FTIR) and DOC analysis at pH 4. FTIR was used for the initial functional group characterization, as well as the comparison of before and after adsorption spectra of the HA and FA. DOC examined the amounts of HA and FA adsorbed …

The Distribution Of Airborne Coal Dust In Soil Profiles Of Norfolk, Va And Its Implication For Arsenic Loading To These Soils, William Joseph Bounds

OES Theses and Dissertations

Norfolk, Virginia is home to the Northern Hemisphere's largest coal terminal the Lamberts Point Docks. The coal loading process of this terminal creates large amounts of coal dust, which subsequently is distributed throughout the local region by atmospheric transport and deposition. While the coal dust itself poses only minor health hazards, certain trace elements within the coal, particularly arsenic, may pose environmental as well as significant health hazards. Within coal, arsenic occurs primarily in the mineral pyrite. As pyrite in the coal dust is subsequently oxidized via exposure to the atmosphere and/or meteoric water, arsenic may be released to the …

Zinc Speculation And Ligand Fluxes In Chesapeake Bay And Elizabeth River Pore Waters, Duncan Glover Byers

Chemistry & Biochemistry Theses & Dissertations

Presented here are the first data on the vertical concentrations, complexation, speciation, and fluxes of total dissolved zinc and zinc complexing ligands, and zinc speciation in sediment pore waters in the Chesapeake Bay and Elizabeth River, Virginia.

Sediment pore waters were collected in mid and southern Chesapeake Bay in November 1997 and in the Elizabeth River (Pinner's Point) in March, April, and July 1998. Flux experiments were conducted in Elizabeth River sediment cores in April and July 1998. [TDZn] and zinc complexation were determined using differential pulse anodic stripping voltammetry at a hanging mercury drop electrode (DPASV-HMDE).

[TDZn] in the …

Effects Of Organic Matter And Iron-Rich Clay On Mobility Of Trace Metals From Flue Dust Contaminated Soil, Scott Ephraim Lewis

OES Theses and Dissertations

The enhanced leaching of trace metals through soil becomes a concern for human health if dissolved trace metals reach groundwater and migrate into a public water system. A serial batch extraction procedure was implemented to determine the effects of Vitagrow © organic matter and Fe-Rich TM clay on the mobility of trace metals (Zn, Pb, and Cd) from a flue dust treated (0, 600, 1200, and 2400 μgig Zn) Appling soil.

The addition of an organic matter (OM) amendment to the Appling soil enhanced Pb mobility and reduced soluble Zn and Cd. In general, average solution concentrations of trace metals …

Analysis Of Lunar Basalt Flows In Oceanus Procellarum Using Clementine Data, Noel William Jackson

OES Theses and Dissertations

Remote sensing analyses of data set taken by Clementine in 1994 permit new observations about mineral distribution on the lunar surface, basalt flow stratigraphy, and thus the geologic evolution of the Moon. The northern section of Oceanus Procellarum contains numerous impact craters which penetrated the basalt and thus can be used as natural probes to estimate the number and thicknesses of flows.

I constructed a mosaic taken in three frequencies ( 415 nm, 750 nm, 950 nm), and a Ratio Image (750/415 = red, 750/950 = green, 415/750 = blue). On such an image, red indicates the iron-poor mature highland …

The Geomorphological History Of An Alluvial Fan Complex In Nelson County, Virginia, Melinda Ann Youngblood

OES Theses and Dissertations

An alluvial fan complex blankets a portion of the Rockfish Valley in Nelson County Virginia, located along the eastern slope of the Blue Ridge Mountains. The seven-km² field area contains three mappable relict alluvial surfaces (Qf1, Qf2, and Qf3) and one modern surface (Qa1), each of which is underlain by fluvial deposits dominated by greenstone and charnokite cobbles. The four surfaces were mapped according to topographic position and degree of stream dissection. Alluvial deposits underlying each surface were characterized using a 3-part clast weathering scale based on greenstone clast weathering rinds and using soil development criteria (clay content, Munsell …

Biostratigraphic Analysis Of Southern Florida's Plio-Pleistocene Shell Beds, Dalton L. Rasmussen

OES Theses and Dissertations

Four molluscan assemblage zones in southern Florida corresponding to the Pinecrest Sand Member of the Tamiami Formation, and the Caloosahatchee, Bermont and Fort Thompson shell beds were identified following quantitative and qualitative analyses of the fossil molluscan fauna. Twenty-eight bulk sediment samples collected from 16 localities across southern Florida were processed for fossil material, and yielded nearly 60,000 specimens belonging to 311 species. A Q-mode cluster analysis compared sediment samples on the basis of 188 species whose abundances had been converted to binary presence-absence form. The cluster analysis was run four times using the Jaccard and Dice similarity coefficients as …

The Effects Of Organic Matter Rich Topsoil On The Germination Growth And Metal Uptake Of Corn (Zea Mays) Grown In Flue Dust Contaminated Soil, Christopher Allen Impellitteri

OES Theses and Dissertations

The large biomass of corn (Zea mays) and promising results from a previous experiment (Chlopecka and Adriano, 1995) concerning metal uptake by corn indicate that corn may be a good candidate for phytoremediation of trace metal contaminated soil. Appling soil (acid, thermic, typic paleudult) was treated with increasing levels of a metal rich flue dust based on Zn concentration (0, 150, 300, 600, 1200, and 2400 mg/kg). Four replicates at each Zn treatment level were either limed to pH 6.3-6.5 and covered with a two inch thick layer of organic matter rich topsoil (OM), unlimed and covered with …